Printing polyester textiles with a disperse dye paste containing an alkyl amide or alkylene diamide



United States Patent Office ABSTRACT OF THE DISCLOSURE An improvedprocess for printing organic hydrophobic textiles with an aqueousprinting paste comprising a nonpolymerizable aqueous paste base and adyestuff selected from dispersed dyes and vat dyes, improvement relatingto the effecting of a deep color with a relatively low fixingtemperature and relatively short fixing time by including within theaqueous printing paste from 0.1-20% by weight of a carboxylic acid amideselected from the formulae /R2 RICON /R2 and R4 C ON wherein R is analiphatic radical of a monocarboxylic acid, R and R are each selectedfrom the group consisting of hydrogen and lower alkyl radicals and R isan aliphatic radical derived from a dicarboxylic acid, the total numberof carbon atoms in the carboxylic acid amide being from 8-22.

This application is a continuation-in-part of Ser. No. 255,100 filedJan. 30, 1963.

This invention relates to a novel printing paste and more particularlyrelates to a printing paste usable for printing organic hydrophobictextiles and a process for printing organic hydrophobic textiles.

Conventionally, when organic hydrophobic textiles have been printed bydispersed dyes or vat dyes, a process has been employed which effectsdyeing by printing a printing paste on the textile and alternatively, ifdesired, the printed textile is subjected to a preliminary drying, andthereafter to a dry heating or steaming operation. A fixing method bydrying is a continuous and effective method, however, it is generallydifficult to advantageously obtain a printed fabric of a deep color bydry heating. To obtain any degree of deep color, it has heretofore beennecessary to employ high temperatures for long periods of time. Suchhigh temperatures for long periods of time, however, suffer from thedisadvantage of producing textiles that are damaged, deterioratedhandling or staining of the non-printed portion of the textile caused bythe sublimation of the dyes. Also, the use of a higher temperature and alonger period unfavorably affects textiles consisting of fibers havingdifferent heat resistances. Similarly, in a dry heating fixing method,when a printing paste blended with a substance known as a carrier hasbeen used, it has been found impossible to obtain a printed textile of asufficiently deep color. Also, in a fixing method by steaming used incase of cellulose triacetate textiles or polyester textiles, thesteaming is carried out batchwise. Therefore, such process cannot be3,519,377 Patented July 7, 1970 employed for large scale production. Ina fixing process by steaming, a substance known as a carrier has beenblended into a printing paste. The effect by the addition of thecarrier, however, has been small and a dyeing of a satisfactorily deepcolor has not been obtained. Moreover, sometimes the added carrierremains in the printed textile and thus the fastness to light of theproduct is greatly lowered.

Accordingly, a principal object of this invention is to provide aprinting paste for printing organic hydrophobic textiles which makes itpossible to obtain dyeing of a sufficiently satisfactory deep color evenwhen a relatively low fixing temperature and/or a relatively shortfixing period are(is) employed.

Yet another object of the present invention is to provide a printingpaste in which a mono-N dicarboxylic acid amide is advantageouslyemployed to make it possible to obtain dyeing of a sufficientlysatisfactory deep color even when a relatively low fixing temperatureand/ or a relatively short fixing period are(is) employed.

Another object of this invention is to provide a process for printingorganic hydrophobic textiles employing a relatively low fixingtemperature and/ or a relatively short fixing period, nevertheless,allowing dyeing of a sufficiently satisfactorily deep color.

Still another object of this invention is to provide a printing pastecapable of being used for the printing of textiles containing fibers ofconsiderably different heat resistance.

Other objects and advantages of this invention Will become apparent fromthe following description.

The printing paste of this invention comprises a paste base, dyes havingaffinity to the textiles to be printed and in an amount of 01-20% byweight based on the Weight of the entire paste of a carboxylic acidamide of the general formulae /R2 /R2 and R4 CON wherein R is analiphatic radical of a monocarboxylic acid; R and R are each selectedfrom the group consisting of hydrogen and lower alkyl radicals; and R isan aliphatic radical derived from a dicarboxylic acid, the total numberof carbon atoms in the carboxylic acid amide being preferable from 8-22.

These materials are hereinafter referred to as thermosol carriers. Thepreferred thermosol carriers are those in which R and R are hydrogen.Examples of such materials include octyllamide, laurylarnide,myristylamide, palmitylamide, stearylamide, adipic amide, azelaic amide,sebacic amide, suberic amide, dodecandioic acid amide andoctadecanedioic amide. Examples of the N-substituted acid amides areN,N-diethyl pentylamide, N-butyllaurylarnide, N,N-dibutylacetamide, N,Ndibutyllaurylamide, N,N-diethylstearylamide, N,N,N,N tetraethyl adipicamide, N,N dibutyl sebacic amide, etc. The preferred thermosol carrierswherein R and R are hydrogen are normally solid and have relatively highboiling point, whereas the N-substituted acid amides are in generalnormally liquid and have lower boiling point. The former gives rise toless bleeding and sharper printing than the latter, and also exhibitsexcellent carrier effects.

In accordance with this invention it has unexpectedly been found thatthe amount of thermosol carrier employed, i.e., from 0.120% by weight onthe total weight of the paste is critical. If amounts less or greaterthan this amount are employed the necessary paste will not be formed,and the unusual and unexpected color fastness and deep color associatedwith low fixing temperature and relatively short fixing period capableof being RiCON employed by the use of the formulations of the presentinvention will not be observed.

As mentioned previously, the printing paste of this invention comprisesa paste base, dyes having affinity to the textiles to be printed and athermosol carrier in an amount of 01-20% by weight based on the weightof the entire paste. Paste bases unstable in this invention are known.The paste base is a non-polymerizable base, i.e., does not polymerizeupon heating. As a paste base, for instance, an aqueous paste of sodiumalginate (solid content: about 6%), sodium salt ofcarboxymethylcellulose (solid content: about 4%), Nafka crystal gum(solid content: about 33%), starch (solid content: about 12% locust beangum (solid content: about 25%) and tragacanth gum (solid content: about6%) may be used. A Yuzen paste consisting of 20 parts of glutinous ricepowder, 20 parts of nonglutinous rice powder, parts of sodium chlorideand 75 parts of water is a preferable base usable in this invention. Anaqueous paste of polyvinyl alcohol may also be employed. Also, anemulsion thickenings are usable.

The printing paste of this invention can be used particularlyadvantageously for printing organic hydrophobic textiles. The textilesto be printed can be in the forms of woven or knitted fabrics, nonwovenfabrics, tow or yarn. These organic hydrophobic textiles can bemanufactured from semi-synthetic fibers such as cellulose acetate andcellulose triacetate fibers or from synthetic fibers such as polyesters,polyvinyl chloride, polyamides, polyacrylonitrile and polypropylenefibers. Also, these textiles can be mixed spun or mixed woven productsof more than one of these organic hydrophobic textiles or mixed productsof these fibers and other natural or manmade fibers. For example,textiles obtained by mix spinning polyethylene terephthalate staplefiber and cott on (or rayon staple fiber) and textiles obtained by mlxspinning polyethylene terephthalate staple fiber, polyvinyl chloridestaple fiber and rayon staple fiber can be advantageously printed by theprinting paste of thls invention.

Dyes usable in the printing paste of this invention are known per se. Solong as they have afiinity to the textiles to be printed, and contain nosolubilrzing sulfonic acid groups, any vat or dispersed dyes can beemployed. Examples of such dyes are Dispersol Fast Yellow G, (CI 11855CI Disperse Yellow 3), Dispersol Fast Scarlet B (CI 11110 CI DisperseRed 1), Fenacet Fast Blue BFN (CI 61505 CI Disperse Blue 3); vat dyessuch as Mikethren Gold Yellow GK (CI 59100 CI Vat Yellow 4), IndanthrenBrilliant Orange GR (CI 71105 CI Vat Orange 7), suprafix paste,Mikethren Brilllant Pink R (CI 73360 CI Vat Red 1), Mikethren Red VioletRH (CI 73385 CI Vat Violet 2), Mikethren Blue GCD (CI 69810 CI Vat Blue14), Mikethren Brilliant Green FFB (CI 59825 CI Vat Green), andMikethren Printing Black B (CI 73830 CI Vat Black 2). Acid dyes andbasic dyes may also be used. The dyes may be applied to polyestertextiles, polyvinyl chloride textiles, polyamrde text les,polyacrylonitrile textiles and polypropylene textiles. Ordinarily, thesedyes are blended in an amount of about 0.1-8% by weight based on theWeight of the entire paste, but it is possible to blend these dyes in anamount of up to 30% by weight as occasion demands.

There is no special restriction on the process of m x ng the paste base,dyes and the thermosol carrier of thls 1nvention. It is possible tomerely add the thermosol carrier to the paste base, but it is preferableto make an emulsion or a dispersion of the thermosol carrier by using aproper emulsifier or a dispersing agent and then adding the emulsion ordispersion to the paste base.

When the printing paste of this invention is printed on textiles andafter a preliminary drying when a fixing by dry heating or steaming iscarried out, the thermosol carrier in the printing paste has a functionof promoting ditfusion of the dyes in the paste layer. Ordinarily, apreliminary drying may be carried out at a temperature of 50100 C. for aperiod ranging from several minutes to several hours. Even during thisperiod, the dyes move onto the surface of textiles in the paste layer.During the process of fixing by dry heating or steaming, dyes rapidlydiifuse in the paste layer, simultaneously or subsequently being dyed tothe textiles. The conditions of dry heating and steaming vary dependingon the kind and the form of textiles to be printed; however, ordinarilya dry heating at a temperature of -220 C. for a period ranging fromseveral seconds to several minutes and a steaming under atmosphericpressure to 1.8 kg./cm. gauge pressure for a period ranging from severalminutes to one hour are proper. Also the higher the temperature of theheat treatment, the shorter the treating period.

In a printing process using the printing paste of this invention,because of the diffusion promoting function of the thermosol carrier inthe printing paste, greater dyeing is promoted than in conventionalprocesses and a print of a deeper color is obtained. Also, in thepresent process, even when a lower temperature of a heat treatment inconventional processes and/or a shorter period than that of conventionalprocesses are(is) employed, a printing efiect equal or greater than theprinting effect in the conventional processes is attained.

In a preferable mode of this invention, it is possible to add aso-called dip dyeing carrier as a dyeing accelerator for the purpose ofincreasing the velocity of diffusion of dyes into textile.

As these carriers, there are, for example, benzoic acid, its derivativessuch as methyl ethyl, propyl, butyl, amyl, phenyl, benzyl, and naphthylbenzoates and m-nitrobenzoic acid; salicylic acid and its derivativessuch as methyl ethyl, butyl, phenyl and benzyl salicylates and phenylp-bromosalicylate; benzenedicarboxylic acid and their derivatives suchas dimethyl diethyl, dibutyl, dioctyl, diphenyl, and dibenzylbenzenedicarboxylates; cinnamic acid and its derivatives such as methyl,ethyl, butyl, phenyl and benzyl cinnamates; ketones such as acetophenonepropiophenone, =benzophenone and 2,4-dihydroxy-acetophenone; phenolssuch as p-nitrophenol, p-chlorophenol, o-chlorophenol, p-bromophenol,2,4,6-trichlorophenol, 2,4,6-tribromophenol and m-cresol; ethers such asanisol, pbromophenyl methyl ether and methyl fl-naphthyl ether;halogenated aroamtic hydrocarbons such as 1, 2, S-trichlorobenzene,a-bromonaphthalene and a-chloronaphthalene; phenylmethane derivativessuch as diphenyldichloromethane, triphenylchloromethane and triphenylcarbinol; diphenyl and its derivatives such as o-phenylphenol,p-phenylphenol, 4,4-dihydroxydiphenyl and 4,4- diaminodiphenyl; andnaphthalene and its derivatives such as a-naphthoic acid, p-naphthoicacid, methyl and ethyl naphthoates, fl-methyl naphthalene and1,2,3,4-tetrahydronaphthalene.

Those skilled in the art can properly and easily select the carrier fordip dyeing to be used according to the kinds of textiles to be printed.

These carriers are added ordinarily in an amount of about 10400% byweight based on the weight of the thermosol carrier. When a thermosolcarrier of this invention and a dip dyeing carrier are used jointly,printing can be carried out even more elfectively.

The following examples are for the explanation of this invention.

EXAMPLE 1 A printing paste of the following composition was printed on afabric of polyethylene terephthalate.

Fenacet Fast Blue 50 Laurylamide 50 Sodium alginate (6% aqueoussolution) 600 Water 300 In preparing the above composition, 50 g. ofFenacet Fast Blue FFN and 300 g. of water mixed. Thereto 50 g. oflaurylamide and 600 g. of sodium alginate (6% aqueous solution) wereadded and mixed.

Thereafter, the fabric was preliminarily dried, and fixed by dry heatingat 190 C. for 60 seconds. Thereafter, the fabric was subjected to areduction clearing at 80 C. for 20 minutes with an aqueous solutioncontaining 0.2% each of NaOH, hydrosulfite and Amirajin. Amirajin is anon-ionic surfactant having the following structural formula:

CnH2n+1 (CH2CH2Oly n, x and y are positive integers. A printed fabrichaving good color fastness and of deep dark blue was obtained.

EXAMPLE 2 A printing paste of the following composition was printed on afabric of polyamide synthetic fiber (nylon 66).

Dispersed Fast Scarlet B 50 Laurylamide 50 Sodium lauryl sulfate 25Water 25 Yuzen paste, Nafka paste (1:1) 600 Water 250 1 Nafka paste isprepared by reacting natural rubbers with hydrochloric acid underpressure and thereafter solubilizing the resultant product.

In preparing the above composition, 50 g. of laurylamide were mixed with25 g. of sodium lauryl sulfate. The mixture was heated to 100 C.Thereafter, 25 g. of water were gradually added thereto and thelaurylamide was dispersed. Next, a printing paste was prepared accordingto the conventional method. Thereafter, the fabric was preliminarilydried, fixed by dry heating at 150 C. for 4 minutes, and rinsed soaped.A printed fabric having good color fastness and a deep scalet color wasobtained.

EXAMPLE 3 A printing paste of the folowing composition prepared bymethod as shown in Example 2 was printed on a knitted fabric ofpolyacrylonitrile.

Dispersol Fast Yellow G 60 Stearylamide 40Triethyleneglycol-mono-laurylether 5 Yuzen paste, Nafka paste (1:1) 600Water 295 Thereafter, the knitted fabric was dried and fixed by dryheating at 140 C. for 7 minutes, followed by rinsing and soaping. Aprinted knitte fabric having good color fastness and a deep yellow colorwas obtained.

EXAMPLE 4 A printing paste of the following composition prepared bymethod shown in Example 2 was printed on a fabric consisting of 65% ofpolyester synthetic fiber and 35% of cotton.

Fenacet Fast Blue FFN 40 Mikethren Blue GCD 40 Strearylamide 25 Sodiumstearyl sulfate 25 Water 50 Sodium alginate (6% aqueous solution) 600Water 200 After the fabric was printed, it was dried and then heattreated at 190 C. for 1 minute. Immediately thereafter, a chemical pasteconsisting of 8 g. of hydrosulfite, 7 g. of NaOH, 3 g. of Betagum J(trademark of a paste produced by Meisei Kagaku Kogyo Co.) and 82 g. ofwater was printed on the fabric by blotch roller and fixed at C. for 40seconds by steaming. Thereafter, the fabric was rinsed, treated at 40 C.for 30 seconds by a 2% aqueous solution of acetic acid, rinsed, treatedat 40 C. for 30 seconds by a 0.7% aqueous solution of hydrogen peroxide,rinsed, soaped and dried.

Thus, the fabric printed with a printing paste added with stearylamidedisplayed a deeper blue color than that of the fabric printed with aprinting paste not added with stearylamide.

EXAMPLE 5 When the stearylamide of Example 4 is rep aced with sebacicamide, the fabric printed with the printing paste added with sebacicamide displays a deeper blue color than that of the fabric with aprinting paste not added with sebacic amide.

EXAMPLE 6 When the stearylamide of Example 4 is replaced withN,N-diethylstearylamide a deeper blue color is also observed.

It will be understood, of course, that the printing pastes of thepresent invention can contain other dyeing assistants such as surfaceactive agents, wetting agents, and solvents for the dyes.

EXAMPLE 7 Printing pastes of the following compositions were printed ona fabric of polyethylene terephthalate.

The fabric was preliminarily dried, and heated at C. for 60 seconds.Thereafter, the fabric was subjected to a reduction clearing at 80 C.for 20 minutes with an aqueous solution containing 0.2% each of NaOH,hydrosulfite and Amirajin.

The color difference of the printed fabric was measured by a colordifference meter and the color difference AE (NBS unit) was calculatedusing a fabric printed with the corresponding paste without a thermosolcarrier as a standard. The fabric printed with paste A showed AE of17.37 whereas the fabric printed with paste B showed AE of 2.86.Further, the bleeding of the latter was greater than that of the formerby about 0.5 mm.

We claim:

1. In a process for the printing of linear polyester textiles with anaqueous printing paste consisting essentially of a non-polymerizableaqueous paste base and a dyestuff selected from the group consisting ofdispersed 7 dyes and vat dyes, said dyes having an afiinity for thetextile, with subsequent fixing and washing of the textile, theimprovement which comprises dyeing the textile a deep color with arelatively low fixing temperature and relatively short fixing time byincluding with said aqueous printing paste from O.120% by weight of acarboxylic acid amide selected from the group consisting of amides ofthe formula /Rz /R2 and Rr-liC ON wherein R is an alkyl radical of afatty monocarboxylic acid, R and R are each selected from the groupconsisting of hydrogen and lower alkyl radicals and R is an alkyleneradical of a dicarboxylic acid, the total number of carbon atoms in thecarboxylic acid amide being from 8-22.

2. The process of claim 1 wherein the carboxylic acid amide is laurylamide.

3. The process of claim 1 wherein the carboxylic acid amide is stearylamide.

RiCON 4. The process of claim 1 wherein the carboxylic acid amide isN,N-diethylstearylamide.

5. The process of claim 1 wherein the carboxylic acid amide is sebacicamide.

References Cited UNITED STATES PATENTS 2,094,609 10/1937 Kritchevsky 8702,225,603 12/1940 Lubs 8-87 2,225,604 12/1940 Lubs et a1. 887 2,290,9457/1942 Dahlen et a1. 8-85 3,120,508 2/1964 Braun et a1. 260-1613,281,201 10/1966 Mauntner 893 XR 2,828,180 3/1958 Sertorio.

OTHER REFERENCES Schwartz et a1.: Surface Active Agents, 1949, vol. I,pp. 212-213, pub. by Interscience Pub. Inc.

20 DONALD LEVY, Primary Examiner US. Cl. X.R.

